CN101796091B - Foam curable by heat - Google Patents

Abstract

The present invention relates to a foam that can be cured by heat, having 10 to 80 vol. % of at least one gas and a compound Z that can be cured by heat, comprising at least one polyurethane polymer of the formula (I) and at least one curing agent B that can be activated by increased temperature. Foams that can be cured in said way are suitable as glues, sealing compounds, or for the production of coatings, particularly as glue that is cured by heat for structural adhesive bonds and for lining in vehicle construction.

Description

Heat-setting foam

Technical field

The present invention relates to as tackiness agent, sealing agent or the Thermocurable foam field for the preparation of coating.

Prior art

The heat-curable epoxy resin compositions of the reaction product of the polyether polyols with reduced unsaturation that comprises isocyanate groups end-blocking and monohydroxy epoxide is known as impelling strength activator, and is for example described in WO 2004/0055092 A1 and WO 2005/007720 A1.This heat-curable epoxy resin composition is particularly suitable as the application of construction adhesive for having high requirements at tool aspect mechanical properties.

For less material consumption and relevant cost savings and/or in order to reduce the reason of weight, and also in order to change the character of composition or for cavity filling is with sound insulation or enhancing, for a long time, to make the mainly composition foaming as tackiness agent or sealing agent.Based on identical reason, it is favourable making foregoing heat-curable epoxy resin composition foaming.

This heat-curable epoxy resin composition be high viscosity and in the situation that using chemistry or pneumatogen, make it up to now foaming, described whipping agent after its application under heat effect before composition is curing or during bring into play their effect.The shortcoming of this foaming process is that the accurate application of foam is almost impossible.The direction that the volume increase of heat-curable composition and the foams that produce after applying by chemistry or pneumatogen expand, can not predict very accurately.The foam expanding can for example make base material to be bonded mutually move or heave from seam, to such an extent as to forms defective the finished product.Because composition requires rising temperature by the expansion of chemistry or pneumatogen, so solidifying with foaming of Thermocurable foam occurs simultaneously, this is again a shortcoming of the method.Thus, on the one hand, before foaming completely, heat-curable epoxy resin compositions may have cured, and for example, when foam is when acting on the sealing agent of seam and seam and do not fill completely due to not satisfied foaming also, this can be very debatable.On the other hand, for example, in the time of bonding two kinds of base materials, after foaming, fixed case is no longer impossible as moved the base material having engaged, and this is because solidifying of composition epoxy resin just started during foaming process.Due to identical, for example so-called finishing (Abziehen), the polishing of rear sealing joints of foaming is also impossible or is at least more difficult.

Another shortcoming of this foam is that the degree of foaming can be difficult to condition and can not check before application.

Invention is described

Therefore the object of the present invention is to provide a kind of the overcome shortcoming of prior art and the Thermocurable foam that can accurately apply.

According to the present invention, this feature by first claim realizes.Wonderful discovery, before application, the Thermocurable foam that foamed is especially suitable for use as tackiness agent, sealing agent or for the preparation of coating.

Especially, the invention has the advantages that, widened that the Application Areas of heat-curable epoxy resin composition and they can also be used cheaply in large area and be to save weight.Another very important advantage is, Thermocurable foam can very accurately apply and in solidification process, keep in fact its shape and structure.Thus, likely also use the Thermocurable foam being formed by composition epoxy resin to prepare to bond highly accurately complex body or sealing seam.Another advantage of the present invention is, the foaming degree of Thermocurable foam can point-device adjusting and can also be prepared the foam with very high gas ratio.The fine adjustment of foaming degree makes therefore can make foam by identical heat-curable composition, and they have different performances and can be used for different objects.

For the preparation of suitable method and direct use heat solidified nature foam subsequently, even make likely during applying, to change the gas content in foam.This is particularly advantageous, because particularly there is no need thus to use more equipment and this using to carry out in the machine applications by means of paint robot, does not need to unload mean for applying with becoming one.

Other side of the present invention is the theme of other independent claim.Particularly preferred embodiment of the present invention is the theme of dependent claims.

Embodiments of the present invention

First the present invention provides a kind of Thermocurable foam, and its at least one gas by 10 to 80% volumes and the polyether polyols with reduced unsaturation that comprises at least one formula (I) and at least one consist of the heat-curable composition Z of the solidifying agent B of the temperature-activated that raises.

In this article, term " foam " refers to by the structure that fill, spherical or that polyhedron-shaped cell forms of the gas by liquid, semiliquid, high viscosity or the restriction of solid cell wall.

With for example polyvalent alcohol of material title or many (gathering) isocyanic ester of " poly-(many) " beginnings, refer in this article the material that formal each molecule comprises the functional group occurring in two or more these titles.

Term " polymer " " in the literature, comprise on the one hand and preparing by polyreaction (addition polymerization, poly-addition, polycondensation), chemically consistent but in the polymerization degree, macromolecular set that molar mass is different with chain long side.This term also comprises the derivative of the described macromolecular set from polyreaction on the other hand, that is obtain by the addition of functional group on for example given macromole or the reaction of replacement and can be chemically consistent or chemically inconsistent compound.This term further also comprises so-called prepolymer, that is its functional group participates in the oligomeric pre-adducts of reactivity that macromole builds.

Term " polyether polyols with reduced unsaturation " comprises all polymkeric substance of preparing by so-called vulcabond-polyaddition.It also comprises those almost or the polymkeric substance of acid esters containing urethane groups not completely.The example of polyether polyols with reduced unsaturation is polyethers-urethane, polyester-polyurethane, polyurethane-polyurea, polyureas, polyester-polyureas, poly-isocyanurate or poly-carbodiimide.

In the polyether polyols with reduced unsaturation of formula (I), R ¹for by the polyether polyols with reduced unsaturation PU1 of linear or branching n1+n2+n3 isocyanate groups end-blocking, after removing the isocyanate groups of all ends.

Radicals R ²the blocking groups for leaving away at the temperature higher than 100 DEG C that each is separate, or the group of formula (II).

Radicals R ³each is separate is the blocking groups of leaving away at the temperature higher than 100 DEG C or the group of formula (II ').

Here radicals R ⁴and R ⁴' each is for optionally comprising heteroatomic aliphatics, alicyclic, aromatic series or araliphatic (p+1)-or (f+1)-valency alkyl.

What p and f were separate is 1,2 or 3.

N1, n2 and n3 are independently 0 to 7 numerical value mutually, and prerequisite is 2≤(n1+n2+n3)≤8.

There is in principle possible very widely blocking groups R ²and R ³and those skilled in the art know a large amount of this blocking groupses, for example from Douglas A.Wick at Progressin Organic Coatings 36 (1999), 148-172 and Progress in OrganicCoatings 41 (2001), the article in 1-83.

Especially, radicals R ²and/or R ³for selecting the group of the group that freely following group forms

with

Here R, ⁵, R ⁶, R ⁷and R ⁸each separate be alkyl or cycloalkyl or aryl or aralkyl or alkylaryl group.Same, R ⁵with R ⁶, or R ⁷and R ⁸can form together the 4-that is optionally the substituted part to 7-ring.

R ⁹, R ⁹' and R ¹⁰each separate be alkyl or aryl or aralkyl or alkaryl or be alkoxyl group or aryloxy or alkoxy aryl, and R ¹¹for alkyl.

In addition R, ¹², R ¹³and R ¹⁴each separate for there are 2 to 5 carbon atoms and can optionally there is two keys or substituted alkylidene group, or be the phenylene of phenylene or hydrogenation.

R ¹⁵, R ¹⁶and R ¹⁸each separate be H or be alkyl or aryl or aromatic alkyl group, and R ¹⁸for aralkyl or be monocycle or the how cyclosubstituted or unsubstituted aromatics group with aromatic hydroxyl optionally.

Certainly it will be apparent for a person skilled in the art that, in the time that the polyether polyols with reduced unsaturation of formula (I) has free isocyanate groups, when in the polyether polyols with reduced unsaturation of formula (I) when n3 ≠ 0, all above-mentioned substituting groups do not allow to comprise hydroxyl, primary amino or secondary amino group, sulfydryl, urea groups or other have the group of reactive hydrogen.

Solidifying agent B is by the temperature-activated raising.Free Dyhard RU 100 is selected in preferred consolidation agent, guanamines, guanidine, the group of aminoguanidine and their derivative composition.In addition, there is the solidifying agent of promoter action, the urea for example replacing, as 3-(the chloro-4-aminomethyl phenyl of 3-)-1,1-dimethyl urea (chlorotoluron) or phenyl dimethyl urea, be in particular rubigan-N, N-dimethyl urea (monuron), 3-phenyl-1,1-dimethyl urea (fenuron) or 3,4-dichlorophenyl-N, N-dimethyl urea (Diuron Tech) is also feasible.In addition can also use, the compound of imidazoles and amine complex class.

Solidifying agent B preferably selects free Dyhard RU 100, guanamines, guanidine, aminoguanidine and their derivative; The urea replacing, particularly 3-(the chloro-4-aminomethyl phenyl of 3-)-1,1-dimethyl urea (chlorotoluron) or phenyl dimethyl urea, be in particular rubigan-N, N-dimethyl urea (monuron), 3-phenyl-1,1-dimethyl urea (fenuron), 3,4-dichlorophenyl-N, N-dimethyl urea (Diuron Tech), and also have the solidifying agent of the group of imidazoles and amine complex composition.

Particularly preferred solidifying agent B is Dyhard RU 100.If the polyether polyols with reduced unsaturation of formula (I) has epoxy group(ing) and isocyanate group simultaneously, solidifying agent B is preferably imido amine (Imidoamin), most preferably be the imide of polyalkylene polyamine, be in particular single imide of polyalkylene polyamine.

If n3 >=2 and 2≤n3≤8 correspondingly in the urethane of formula (I), solidifying agent B is the solidifying agent for isocyanic ester.The closed process of this solidifying agent B can be chemical nature or physical nature.The example of the solidifying agent of suitable chemistry sealing is the complex compound that is connected to the polyamines on metal, particularly methylenedianiline (MDA) and sodium-chlor by complex bonds.This complex compound is conventionally by summary-type (MDA) ₃naCl describes.Point dispersion that suitable type can be used as in phthalic acid diethylhexyl ester obtains, and its trade name is from Chemtura Corp., USA's

this complex compound decomposes with the speed increasing along with the increase of temperature in the time being heated to 80 to 160 DEG C, discharges thus the solidifying agent of methylenedianiline as activation.The example of the solidifying agent of physical containment is the solidifying agent of microencapsulation.Be particularly suitable for taking the form of microencapsulation as the material of solidifying agent as dibasic alcohol or polyvalent alcohol more, for example 1, 2-ethylene glycol, 1, 2-and 1, ammediol, neopentyl glycol, Diethylene Glycol, triethylene glycol, the dipropylene glycol of isomery and tripropylene glycol, the butyleneglycol of isomery, pentanediol, hexylene glycol, heptanediol, ethohexadiol, nonanediol, decanediol, undecane glycol, 1, 3-and 1, 4-cyclohexanedimethanol, Hydrogenated Bisphenol A, dimerization fatty alcohol, 1, 1, 1-trimethylolethane, 1, 1, 1-TriMethylolPropane(TMP), glycerol, tetramethylolmethane, sugar alcohol, the low-molecular-weight alkoxylated polymerization product of above-mentioned dibasic alcohol or more polyvalent alcohol, such as diglycol terephthalate of short chain polyester polyvalent alcohol, aliphatics, the alicyclic and amino alcohol of aromatic series, for example thanomin, Propanolamine, butanolamine, N-Mono Methyl Ethanol Amine, diethanolamine, trolamine, the hydrazides of dicarboxylic acid, aliphatic polyamine, for example ethylene diamine, 1, 2-and 1, 3-propylene diamine, 2-methyl isophthalic acid, 2-propylene diamine, 2, 2-dimethyl-1, 3-propylene diamine, 1, 3-and 1, 4-butanediamine, 1, 3-and 1, 5-pentamethylene diamine, 1, 6-hexamethylene-diamine, 2, 2, 4-and 2, 4, 4-trimethylhexamethylenediamine and their mixture, 1, 7-heptamethylene diamine, 1, 8-octamethylenediamine, 4-aminomethyl-1,2, 8-octamethylenediamine, 1, 9-nonamethylene diamine, 1, 10-decamethylene diamine, 1, 11-undecane diamines, 1, 12-dodecane diamines, methyl-bis--(3-aminopropyl) amine, 1, 5-diamino-2-methylpentane (MPMD), 1, 3-1,5-DAP (DAMP), 2, 5-dimethyl-1, 6-hexamethylene-diamine, dimer (fatty acid) yl diamines, alicyclic polyamine, for example 1, 2-, 1, 3-and 1, 4-diamino-cyclohexane, two-(4-aminocyclohexyl) methane, two-(4-amino-3-methylcyclohexyl) methane, two-(4-amino-3-ethyl cyclohexyl) methane, two-(4-amino-3, 5-Dimethylcyclohexyl) methyl, 1-amino-3-amino methyl-3, 5, 5-trimethyl-cyclohexane (=isophorone diamine or IPDA), 2-and 4-methyl isophthalic acid, 3-diamino-cyclohexane and their mixture, 1, 3-and 1, 4-pair-(amino methyl) hexanaphthene, 1-cyclohexyl amino-3-aminopropane, 2, 5 (2, 6)-bis--(amino methyl)-dicyclo [2.2.1] heptane (NBDA, by Mitsui Chemicals, Japan preparation), 3 (4), 8 (9)-bis--(amino methyl)-tri-encircle [5.2.1.0 ^2,6] decane, Isosorbide-5-Nitrae-diamino-2,2,6-trimethyl-cyclohexane (TMCDA), 3,9-is two-(3-aminopropyl)-2,4,8,10-tetra-oxaspiros [5.5] undecane, 1,3-and Isosorbide-5-Nitrae-xylylene amine, the aliphatic polyamine that comprises ether, for example two-(2-amino-ethyl) ethers, 4,7-dioxadecane-1,10-diamines, 4,9-dioxa dodecane-1,12-diamines and their higher oligopolymer, have two or three amino polyoxyalkylene polyamines, and it can be for example with trade name

(by Huntsman International, LLC, prepared by USA) and obtain, aromatic polyamine, for example methylenedianiline, diamino-diphenyl ether, diamino diphenyl sulfone, the phenylenediamine of isomery, amino-diphenyl-amine.Preferably described aliphatics, alicyclic and aromatic polyamine.The microencapsulation of these solidifying agent can be undertaken by the one in usual method, for example by spraying be dried, interfacial polymerization, cohesion, dipping or centrifugal method, bed process, vacuum microencapsulation or static microcapsule.The micro-capsule so obtaining has the granularity of 0.1 to 100 μ m especially, is preferably 0.3 to 50 μ m.When the size of micro-capsule should make to heat on the one hand, they are effectively opened, and obtain best homogeneity on the other hand and also therefore obtain the cohesive strength of foam after solidifying.In addition, they must not have any disadvantageous effect to the sticking property of foam.Can consider for the material of capsule shell it is to be insoluble to polymkeric substance solidifying agent to be packaged and that there are 40 to 200 DEG C of fusing points.The example of suitable polymkeric substance is chloroflo, polyethylene wax, wax ester, polyester, polymeric amide, polyacrylic ester, the multiple mixture in polymethacrylate or these polymkeric substance.

Based on the gross weight of foam, the ratio of solidifying agent B is preferably 0.05 to 8% weight, and it is in particular 0.1 to 6% weight, more preferably 0.2 to 5% weight.

In this article, term " solidifying agent " also comprises the compound of Catalyst & Catalysis.In this case, it will be apparent to one skilled in the art that the ratio of solidifying agent B is arranged in the lower region of described numerical range in whole foam in the time that the compound of catalyzer or katalysis is used as solidifying agent B.Corresponding therewith, in the time that solidifying agent B is the solidifying agent with the stoichiometry specific consumption of the reactive group of the polyether polyols with reduced unsaturation to formula (I), this ratio is arranged in more top numerical range, be typically 0.5 to 8% weight, be in particular 1 to 6% weight, be preferably 2.5 to 5% weight, and in the situation of catalyzer, this ratio will be lower, be typically 0.05 to 2% weight, be in particular 0.1 to 1% weight, be preferably 0.2 to 0.75% weight, in each case equal gross weight meters based on foam.

R ¹based on polyether polyols with reduced unsaturation PU1 can there is the polymkeric substance Q of terminal amino group, thiol group or hydroxyl by least one polyisocyanates with by least one _pMand/or by the polyphenol Q optionally replacing _pPpreparation.

Suitable polyisocyanates is in particular vulcabond and triisocyanate.

Suitable vulcabond is aliphatics, alicyclic, aromatic series or araliphatic vulcabond, particularly common commercially available product, for example methylenediphenyl diisocyanates (MDI), hexamethylene diisocyanate (HDI), tolylene diisocyanate (TDI), tolidine vulcabond (TODI), isophorone diisocyanate (IPDI), trimethyl hexamethylene diisocyanate (TMDI), 2, 5-or 2, 6-pair-(isocyanato methyl)-dicyclo [2.2.1] heptane, 1, 5-naphthalene diisocyanate (NDI), dicyclohexyl methyl vulcabond (H ₁₂mDI), to phenylene vulcabond (PPDI), adjacent tetramethyl-eylylene diisocyanate (TMXDI) etc., and also comprise their dimer.The preferred scheme providing is HDI, IPDI, MDI or TDI.

Suitable triisocyanate is tripolymer, allophanate or the biuret, the particularly chlorinated isocyanurates of the vulcabond described in earlier paragraphs and biuret of aliphatics, alicyclic, aromatic series or araliphatic vulcabond.

Certainly, also likely use the suitable mixture of vulcabond or triisocyanate.

As the polymkeric substance Q with terminal amino group, thiol group or hydroxyl _pM, specially suitable is the polymkeric substance Q with two or three terminal amino groups, thiol group or hydroxyl _pM.

Polymkeric substance Q _pMfavourable have 300 equivalent weights to 6000g/ equivalent NCO-reactive group, is in particular 600 to 4000, is preferably 700 to 2200.

Suitable polymkeric substance Q _pMfor polyvalent alcohol, for example following polyvalent alcohol or their any mixture of being purchased:

-polyoxyalkylene polyols, also referred to as polyether glycol, it is oxyethane, 1,2-propylene oxide, 1,2-or 2, the polymerisate of 3-butylene oxide ring, tetrahydrofuran (THF) or its mixture, and carry out polymerization by means of the starter molecules (Startermolek ü ls) with two or three reactive hydrogen atoms in may situation, for example water of described starter molecules or there is the compound of two or three OH groups.Polyoxyalkylene glycol can have different degree of unsaturation (measure and provide with the milliequivalent degree of unsaturation (mEq/g) of every gram of polyvalent alcohol according to ASTM D-2849-69).Those with low-unsaturation-degree are for example by means of so-called bimetallic cyanide complex catalyst (dmc catalyst) preparation, and those with higher degree of unsaturation are for example prepared as NaOH, KOH, CsOH or alkali metal alcoholates by means of anionic catalyst.

Specially suitable is have lower than the degree of unsaturation of 0.02mEq/g and have 1000-30, the polyoxyalkylene glycol of the molecular weight of 000g/mol scope or polyoxyalkylene triol, and there is 400-8, polyoxygenated ethylidene glycol, polyoxygenated ethylidene triol, polyoxygenated trimethylene glycol and the polyoxygenated propylidene triol of the molecular weight of 000g/mol scope." molecular weight " always refers to average molecular mass Mn in this article.

Similarly, specially suitable is so-called oxyethane-end-blocking (" EO-end-blocking ", ethylene oxide end-blocking) polyoxygenated propylidene polyvalent alcohol.The latter is special polyoxygenated propylidene-polyoxygenated ethylidene-polyvalent alcohol, it for example obtains by the following method: after described poly-propoxylation reaction finishes, pure polyoxygenated propylidene polyvalent alcohol, particularly polyoxygenated trimethylene glycol and polyoxygenated propylidene triol are also made it have to primary hydroxyl thus by the further alkoxylate of oxyethane.

-styrene-acrylonitrile-or the polyether glycol of vinyl cyanide-methyl methacrylate-grafting.

-polyester polyol, also referred to as oligomer ester alcohol, for example by two for example, to trivalent alcohol (1, 2-ethylene glycol, Diethylene Glycol, 1, 2-propylene glycol, dipropylene glycol, 1, 4-butyleneglycol, 1, 5-pentanediol, 1, 6-hexylene glycol, neopentyl glycol, glycerine, 1, 1, the mixture of 1-TriMethylolPropane(TMP) or aforementioned alcohol) and organic dicarboxylic acid or its acid anhydrides or ester (for example succsinic acid, pentanedioic acid, hexanodioic acid, suberic acid, nonane diacid, sebacic acid, dodecanedicarboxylic acid, toxilic acid, fumaric acid, phthalic acid, m-phthalic acid, terephthalic acid and hexahydrophthalic acid, or the mixture of aforementioned acid) prepare, and the polyester polyol being formed by lactone (for example, by 6-caprolactone).

-polycarbonate polyol, for example by as above-mentioned those for building alcohol and the dialkyl carbonate of polyester polyol, diaryl carbonate or phosgene reaction available those.

-polyacrylate polyol and polymethacrylate polyvalent alcohol.

-poly-hydrocarbon polyvalent alcohol, also referred to as oligomeric hydrocarbon polymer alcohol (Oligohydrocarbonole), the for example ethylene-propylene of poly-hydroxy official energy-, ethene-butylene-or ethylene-propylene-diene-multipolymer, for example they can be made by Kraton Polymers company, or poly-hydroxy official can by diene as 1, 3-divinyl or diene mixture and vinyl monomer are as vinylbenzene, the multipolymer that vinyl cyanide or iso-butylene obtain, or the polybutadiene polyol of poly-hydroxy official energy, for example, by 1, those that the copolymerization of 3-divinyl and vinyl carbinol makes and they also can be hydrogenated.

-poly-hydroxy official can acrylonitrile/butadiene multipolymer, for example by the acrylonitrile/butadiene multipolymer of oxirane or amino alcohol and carboxyl termination (commercial can be from Emerald PerformanceMaterials, LLC, USA company is with trade(brand)name

obtain) can make those.

Polymkeric substance Q _pMadvantageously, for thering is two senses of the 300 OH equivalent weights to 6000g/OH equivalent or the polyvalent alcohol of higher official energy, be in particular 600 to 4000g/OH equivalent, be preferably 700 to 2200g/OH equivalent.In addition, polyvalent alcohol advantageously selects free polyoxyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol-segmented copolymer, polytetramethylene glycol, hydroxy-end capped polyhutadiene, hydroxy-end capped butadiene/acrylonitrile copolymer, hydroxy-end capped synthetic rubber, the group of the compositions of mixtures of their hydrogenated products and these polyvalent alcohols.

In addition, as polymkeric substance Q _pMalso likely use amino-terminated polyvinyl ether two senses or higher official's energy, polypropylene ether, for example, by Huntsman International, LLC, USA is with trade(brand)name

those of the commercially available acquisition of selling, polybutene ether, polyhutadiene, butadiene/acrylonitrile copolymer, for example, from Emerald PerformanceMaterials, LLC, USA is with trade(brand)name

those of commercially available acquisition, and also have other amino-terminated synthetic rubber or the mixture of described component.

Polymkeric substance Q _pMcan also be chainpropagation, for example its reaction that can pass through in the manner known to persons skilled in the art polyamine, polyvalent alcohol and polyisocyanates, particularly diamines, glycol and vulcabond be carried out.

Conventionally advantageously guarantee and guarantee especially for the polyether polyols with reduced unsaturation of chainpropagation for polyether polyols with reduced unsaturation PU1, described polymkeric substance does not have too high viscosity, particularly in the time that the compound of higher official's energy is used for to chainpropagation, because this reaction of polymkeric substance or the application of composition that can make them be converted into formula (I) become more difficult.

As polymkeric substance Q _pMpreferably there is the polyvalent alcohol of the molecular weight within the scope of 600 to 6000g/mol, it selects free polyoxyethylene glycol, polypropylene glycol, polyethylene glycol-propylene glycol-block polymer, polytetramethylene glycol, hydroxy-end capped polyhutadiene, the group of hydroxy-end capped perbutan and their compositions of mixtures.

Particularly preferred polymkeric substance Q _pMfor thering is C ₂-C ₆-alkylidene group or there is the C of mixing ₂-C ₆-alkylidene group and by amino, thiol group or preferably hydroxy-end capped α, alpha, omega-dihydroxy polyalkylene glycol.The particularly preferred scheme providing is polypropylene glycol or polytetramethylene glycol.Also scheme is very particularly preferably hydroxy-end capped polyoxybutylene.

Suitable polyphenol Q _pPbe in particular dihydric phenol, trihydric phenol and tetrahydric phenol.This is interpreted as to be not only pure phenol, if the suitable phenol that also comprises replacement here.The type replacing can be very various.Especially, be wherein interpreted as replacing on the aromatic nucleus directly connecting at phenol OH group.In addition, " phenol " not only refers to monocyclic aromatic compound, also refers to have aromatic series many rings or that condense or the heteroaromatic compound of the phenol OH base being directly connected on aromatic substance or heteroaromatic compound.Especially, the type of this replacement and position influence be used to form polyether polyols with reduced unsaturation PU1 required with the reacting of isocyanic ester.

Dihydric phenol and trihydric phenol are specially suitable.Suitable dihydric phenol or trihydric phenol are for example 1, 4-dihydroxy-benzene, 1, 3-dihydroxy-benzene, 1, 2-dihydroxy-benzene, 1, 3-orcin, 3, 5-resorcylic acid ester, 2, 2-bis-(4-hydroxy phenyl) propane (=dihydroxyphenyl propane), two (4-hydroxy phenyl) methane (=Bisphenol F), two (4-hydroxy phenyl) sulfones (=bisphenol S), naphthoresorcinol, dihydroxy naphthlene, dihydroxyanthraquinone, dihydroxybiphenyl, 3, 3-bis-(p-hydroxybenzene) phthalide, 5, 5-bis-(4-hydroxy phenyl) six hydrogen-4, 7-methane indane, phenolphthalein, fluorescein, 4, 4 '-[two (hydroxy phenyl)-1, 3-phenylene two (1-methyl ethylidene)] (=bis-phenol M), 4, 4 '-[two (hydroxy phenyl)-1, 4-phenylene two (1-methyl ethylidene)] (=bis-phenol P), 2, 2 '-diallyl bisphenol, react dihydric phenol and the xylenol of preparation with diisopropylidene benzene by phenol or cresols, Phloroglucinol, gallic acid ester, there are whole isomer of the linear varnish of 2.0 phenol to 3.5OH-functionality or the linear varnish of cresols (Kresolnovolacke) and above-claimed cpd.

Preferably reacting the dihydric phenol prepared and xylenol with diisopropylidene benzene by phenol or cresols has as the chemical structural formula for the cresols illustrating as follows as an example correspondingly:

The bis-phenol of the difficult volatilization of particularly preferred scheme.Dihydroxyphenyl propane, bis-phenol M, bisphenol S and 2,2 '-diallyl bisphenol is most preferred.

Q _pPpreferably there are two or three phenolic group groups.

In first embodiment, polyether polyols with reduced unsaturation PU1 is by least one vulcabond or triisocyanate and by the polymkeric substance Q of amino, thiol group or hydroxyl with end _pMpreparation.This polyether polyols with reduced unsaturation PU1 is prepared in polyurethane field mode known to the skilled, particularly by using relative polymkeric substance Q _pMamino, thiol group or hydroxy chemical measure the preparation of excessive vulcabond or triisocyanate.

In second embodiment, polyether polyols with reduced unsaturation PU1 is by least one vulcabond or triisocyanate and by the polyphenol Q optionally replacing _pPpreparation.Polyether polyols with reduced unsaturation PU1 is prepared in polyurethane field mode known to the skilled, special in using relative polyphenol Q _pPexcessive vulcabond or the triisocyanate preparation of phenolic group group stoichiometry.

In the 3rd embodiment, polyether polyols with reduced unsaturation PU1 is by least one vulcabond or triisocyanate and by the polymkeric substance Q of amino, thiol group or hydroxyl with end _pMand by the polyphenol Q optionally replacing _pPpreparation.Serve as reasons at least one vulcabond or triisocyanate and by the polymkeric substance Q of amino, thiol group or hydroxyl with end _pMand/or by the polyphenol Q optionally replacing _pPprepare polyether polyols with reduced unsaturation PU1, have multiple possible approaches available.

In first method, refer to " one kettle way " here, make at least one polyphenol Q _pPwith at least one polymkeric substance Q _pMmixture react in the excessive mode of isocyanic ester with at least one vulcabond or triisocyanate.

In the second approach, refer to " two-step approach I " here, make at least one polyphenol Q _pPwith at least one vulcabond or triisocyanate reacts in the excessive mode of isocyanic ester and afterwards with at least one polymkeric substance Q _pMreact in the mode that stoichiometry is in shortage.

Finally, in the third method, refer to " two-step approach II " here, make at least one polymkeric substance Q _pMwith at least one vulcabond or triisocyanate reacts in the excessive mode of isocyanic ester and afterwards with at least one polyphenol Q _pPreact in the mode that stoichiometry is in shortage.

These three kinds of methods produced there is same composition but aspect their structural unit sequence different isocyanate-terminated polyether polyols with reduced unsaturation PU1.Three kinds of all methods are all suitable, but preferred " two-step approach II ".

If the isocyanate-terminated polyether polyols with reduced unsaturation PU1 describing is made up of the component of two senses, find polymkeric substance Q _pM/ polyphenol Q _pPequivalence ratio preferably exceed 1.5, and polyisocyanates/(polyphenol Q _pP+ polymkeric substance Q _pM) equivalence ratio preferably exceed 1.2.

If the average functionality of component used exceedes 2, can there is the phenomenon of molecular weight rising faster than the situation of pure two functionality.The boundary value that it will be apparent to those skilled in the art that possible equivalence ratio depends on greatly, the polymkeric substance Q whether selecting _pM, polyphenol Q _pP, the multiple functionality with > 2 in polyisocyanates or mentioned component.Regulate different equivalence ratios according to different situations respectively, its boundary value is determined and must be determined by experiment by different situations by the polymer viscosity of last gained.

Polyether polyols with reduced unsaturation PU1 preferably has elastic characteristic and show≤glass transition temperature Tg of 0 DEG C.

The polyether polyols with reduced unsaturation of formula (I) can be by thering is formula (III) if polyether polyols with reduced unsaturation PU1 and suitable, the reactive compound R of NCO- ²-H and/or R ³-H makes.

Radicals R ²be preferably group and the radicals R of formula (II) ³be preferably the group of formula (II ').The polyether polyols with reduced unsaturation of this preferred formula (I) can the polyether polyols with reduced unsaturation PU1 of through type (III) and the monohydroxy epoxy compounds of formula (IV) or formula (IV ') react preparation.

The monohydroxy epoxy compounds of formula (IV) or formula (IV ') has 1,2 or 3 epoxide group.The hydroxyl of the monohydroxy epoxy compounds of this formula (IV) or formula (IV ') can be primary hydroxyl or secondary hydroxyl.

This monohydroxy epoxy compounds for example can react by polyvalent alcohol preparation with Epicholorohydrin.According to reaction process, the corresponding monohydroxy epoxy compounds that also forms different concns in the reacting of polyfunctional alcohol and Epicholorohydrin is as by product.They can separate by conventional lock out operation.But conventionally, use by completely transforming and become the polyvalent alcohol product mixtures that form, that obtain in the Racemic glycidol glycosylation reaction of polyvalent alcohol of glycidyl ether enough with partial reaction.The example of this monohydroxy epoxy compounds is butyleneglycol monoglycidyl ether (being contained in butanediol diglycidyl ether), hexylene glycol monoglycidyl ether (being contained in hexanediol diglycidyl ether), cyclohexanedimethanol glycidyl ether, TriMethylolPropane(TMP) diglycidylether (to be included in the form of mixtures in trihydroxymethylpropanyltri diglycidyl ether), glycerin diglycidyl ether (to be included in the form of mixtures in the mixture of T 55), tetramethylolmethane triglycidyl ether (to be included in the form of mixtures in tetramethylolmethane four glycidyl ethers).The preferred version providing is to use with the TriMethylolPropane(TMP) diglycidylether to occur relatively at high proportion in the trihydroxymethylpropanyltri diglycidyl ether of preparing in routine.

But also likely use other similar monohydroxy epoxy compounds, particularly Racemic glycidol, 3-glycidoxypropyl benzylalcohol or methylol cyclohexane oxide.The preferred method giving be with about 15% concentration be included in business common, by dihydroxyphenyl propane (R=CH ₃) and the liquid epoxies prepared of Epicholorohydrin in the beta-hydroxy ether of formula (V), and the beta-hydroxy ether of the corresponding formula (V) forming in the reacting of the mixture of Bisphenol F (R=H) or dihydroxyphenyl propane and Bisphenol F and Epicholorohydrin.

The preferred version giving is the distillation residue that obtain in high purity, in the preparation of liquid epoxies of distillation.This distillation residue have than commercially available without distillation liquid epoxies double until the epoxide of the hydroxyl of three times of concentration.In addition, also can use the various epoxide with beta-hydroxy ether group that react preparation by (gathering) epoxide with simple function nucleophilic reagent for example carboxylic acid, phenol, mercaptan or secondary amine lower than stoichiometry.

The free uncle of the monohydroxy epoxy compounds of formula (IV) or formula (IV ') or secondary OH functional group allow there be enough reacting with the blocked isocyanate groups of polymkeric substance, and the while needn't be used out-of-proportion excessive epoxide component.

Polyether polyols with reduced unsaturation PU1 for formula (III) generates wherein n3=0, R ²≠ R ³the reaction of polyether polyols with reduced unsaturation of formula (I), can use together or sequentially R ²h and R ³h.The reaction of order has advantages of that reaction can easier control to such an extent as to reduce and form symmetrical adducts.In consecutive reaction for favourable the using to ensure that all NCO groups are all reacted away with the excessive amount of stoichiometry of compound of second step.

The ratio of the polyether polyols with reduced unsaturation of formula (I) is preferably based on the gross weight of foam and counts 5 to 50% weight, is in particular 10 to 40% weight, is preferably 15 to 35% weight.

Heat-curable composition Z can be extra comprise that at least one has the epoxy resin A of the average more than one epoxide group of per molecule.

Epoxy resin A is preferably liquid epoxies or solid epoxy.Term " solid epoxy " word is that epoxide those skilled in the art are known and contrast use with " liquid epoxies ".The glass transition temperature Tg of solid resin is higher than room temperature (23 ± 1 DEG C), and they can at room temperature pulverize to obtain the powder with the ability of toppling over.

Preferred solid epoxy has following formula (VI)

Here substituent R ' and R " each is separate is H or CH ₃.In addition, index s is >=1.5, is in particular 2 to 12.

This solid epoxy can be for example by Dow Chemical Company, USA, and by Huntsman International, LLC, USA or by Hexion Specialty ChamicalsInc., USA is commercially available.

The compound with the formula (VI) of the index s in 1 to 1.5 scope is called semi-solid epoxy resin by those skilled in the art.For the purposes of the present invention, regard equally them as solid resin.But the preferred scheme of the solid epoxy providing is narrowly that its Exponential s is >=1.5.

Preferred liquid epoxies has following formula (VII)

Here, " each is separate is H or CH to substituent R " ' and R " ₃.In addition, index r is 0 to 1.Preferred liquid epoxies has≤0.2 r value.

Therefore be preferably the diglycidylether (DGEBA) of dihydroxyphenyl propane, the diglycidylether of Bisphenol F or dihydroxyphenyl propane/F.Title " A/F " referred to herein as and in preparation, is used as the formaldehyde of original material and the mixture of acetone.The commercially available acquisition of this liquid resin, for example its trade name is from Huntsman International, LLC, USA company

or from The Dow ChemicalCompany, USA company

or

or from HexionSpecialty Chamicals Inc., the trade name of USA company is

or

Epoxy resin A is preferably the liquid epoxies of formula (VII).At one, also in preferred embodiment, Thermocurable foam comprises the liquid epoxies of at least one formula (VII) and the solid epoxy of at least one formula (VI).

The gross weight that the ratio of epoxy resin A is preferably based on foam is 2 to 80% weight, is in particular 5 to 70% weight, is preferably 5.1 to 70% weight, more preferably 7 to 60% weight.

In first preferred embodiment, the composition Z of Thermocurable foam has wherein n3=0, radicals R as described above ²for group and the radicals R of formula (II) ³for the polyether polyols with reduced unsaturation of the formula (I) of the group of formula (II ').In addition, in this first embodiment, Thermocurable foam has at least one epoxy resin A.

In second embodiment, the composition Z of Thermocurable foam has wherein n1, the polyether polyols with reduced unsaturation of the formula (I) of n2 and n3 ≠ 0.In addition, in this second embodiment, Thermocurable foam has at least one epoxy resin A.

It will be apparent to those skilled in the art that the isocyanate groups that is present in composition Z can with the hydroxyl reaction of the epoxy resin A that may exist.This reaction is favourable in some cases and contributes to pliable and toughization and contribute to the tough property improvement of the foam after thermofixation.

The gas being contained in Thermocurable foam is selected from nitrogen (N ₂), carbonic acid gas (CO ₂), hydrogen (H ₂), carbon monoxide (CO), laughing gas (N ₂o), any mixture of rare gas and these gases and gaseous mixture are as air.Nitrogen or air are specially suitable.The preferred version providing is air.This gas can be drying or undried.Preferably drying of this gas.

In Thermocurable foam, gas is encapsulated in chamber, and this chamber is evenly distributed in foam.

Composition Z can comprise or not comprise chemistry or pneumatogen extraly.What be called chemical foaming agent is the material that forms or decomposite gaseous substance under the effect of heat, electromagnetic radiation or chemical reagent.This material is in particular azodicarboxy acid amides, sulfonyl hydrazide, supercarbonate or carbonate.As pneumatogen, for example can use the compound that is converted into gaseous state state of aggregation in the time changing temperature, pressure or volume, particularly when temperature increases or when pressure decreased, and therefore due to volumetric expansion formation foamy structure.This pneumatogen is in particular the gas that injects or be mixed into the composition under pressure with liquid state or supercritical state, or the liquid evaporating at elevated temperatures.In addition the gas or the low-boiling point liquid that are incorporated in composition with microencapsulation form, also can be used as pneumatogen.

The gross weight of the ratio of whipping agent based on foam is 0.1 to 3% weight in respect of profit.

If by heating under bring into play their effect whipping agent for the preparation of Thermocurable foam, should be noted that and will make the solidification value of blowing temperature lower than Thermocurable foam, this be because otherwise foam in foaming process can solidify.

Whipping agent is used in particular in composition Z or in Thermocurable foam, during curing to make Thermocurable foam post-foaming.Composition Z and Thermocurable foam be not preferably containing chemical foaming agent.

Thermocurable foam can also contain the thixotropic agent C based on urea derivatives.The derivative of this urea is in particular the reaction product of aromatic monomer vulcabond and fatty amine compound.Also can make multiple different monomeric diisocyanate react with multiple fatty amine compound with one or more fatty amine compounds or monosomy vulcabond completely.Have been found that methylenediphenyl diisocyanates (MDI) and the reaction product of butylamine are particularly advantageous.

Urea derivatives is preferably present in solid support material.Solid support material can be softening agent, particularly phthalic ester or adipic acid ester, is preferably phthalic acid diiso decyl ester (DIDP) or Octyl adipate (DOA).Described carrier agent can also the diffusible carrier agent of right and wrong.In order to ensure that solidifying rear unreacted component moves as few as possible, this is preferred.The polyether polyols with reduced unsaturation of sealing is preferably as non-dispersive carrier agent.

In patent application EP 1 152 019 A1, describe the preparation of this preferred urea derivatives and solid support material in detail.Solid support material advantageously for the polyether polyols with reduced unsaturation PU2, the particularly polyether glycol by trifunctional of sealing react with IPDI and afterwards terminal isocyanate group roll into a ball with ε-caprolactam and seal and obtain.

The gross weight of the overall proportion of thixotropic agent C based on foam is 0 to 40% weight in respect of profit, is preferably 5 to 25% weight.The weight ratio of urea derivatives and the optional carrier agent existing preferably, in the scope of 0.02: 1 to 1: 1, is in particular between 0.05: 1 and 0.3: 1.

Thermocurable foam preferably also contains fluid rubber D, and it is preferably the polymkeric substance of carboxyl or epoxy group(ing) end-blocking.

In another embodiment, this fluid rubber D is the acrylonitrile/butadiene multipolymer of carboxyl or epoxy group(ing) end-blocking or its derivative.This fluid rubber is to be for example commercially available, and its trade name is from Emerald Performance Materials, LLC, USA's

cTBN and CTBNX and ETBN.Suitable derivative is in particular the elastomer-modified polymkeric substance with epoxide group, as with product line

be preferably selected from product line from Schill+Seilacher Gruppe, those of the commercially available acquisition of Deutschland, or with product line

from Hanse Chemie AG, those of the commercially available acquisition of Germany.

In another embodiment, this fluid rubber D is completely with liquid epoxies is mixable and the de-liquid polyacrylate rubber that mixes formation fine droplet just in the time that epoxy matrix material is solidified only.This liquid polyacrylate rubber can be for example from Rohm and Haas Co., and USA is to obtain under trade(brand)name 20208-XPA.

It will be apparent to those skilled in the art that nature can also use the mixture of the acrylonitrile/butadiene multipolymer of the mixture of fluid rubber, particularly carboxyl or epoxy group(ing) end-blocking or the polyether polyols with reduced unsaturation of its derivative and epoxy group(ing) end-blocking.

Fluid rubber D favourable taking as 1 to 35% weight of the gross weight based on foam, be in particular 1 to 25% weight amount use.

Thermocurable foam preferably additionally also comprises solid toughness activator E.Here and hereinafter, " toughness activator " word refers to the additive adding in epoxy matrix material, its gross weight meter based on foam, even with 0.1 to 15% weight, particularly little addition of 0.5 to 8% weight, can affect the remarkable increase of toughness and therefore can before matrix is cut off or ruptured, absorb higher bending, stretching, impact or collision stress.

In first embodiment, solid toughness activator E is the layer mineral E1 of organic ion exchange.

The layer mineral E1 of ion-exchange can be the layer mineral E1c of cationic exchange or the layer mineral E1a of anionresin.

The layer mineral E1c of cationic exchange is herein obtained by the layer mineral E1 ' that wherein at least a portion positively charged ion has been exchanged by organic cation.Particularly those,, at US5, mention in 707,439 or US6,197,849 the example of the layer mineral E1c of this cationic exchange.Those files have also been described the method for the layer mineral E1c that produces these cationic exchange.Preferably using layered silicate as layer mineral E1 ".Layer mineral E1 ' is described in as US6,197,849 the 2nd hurdles, the phyllosilicate in the 38th row to the 3 hurdles the 5th row, and wilkinite particularly.Layer mineral E1 ' as kaolinite or montmorillonite or hectorite or illite verified suitable especially.

At least a portion positively charged ion of layer mineral E1 ' is replaced by organic cation.The example of this cationoid is n-octyl ammonium, trimethyldodecane base ammonium, dimethyl dodecyl ammonium or two (hydroxyethyl) octadecyl ammonium or can be from the like derivatives of natural fat and the oil amine that obtain; Or guanidine positively charged ion or amidine (Amidinium) positively charged ion; Or the positively charged ion of the N-substitutive derivative of tetramethyleneimine, piperidines, piperazine, morpholine, thiomorpholine; Or the positively charged ion of Isosorbide-5-Nitrae-diazo bicyclic [2.2.2] octane (DABCO) and 1-azabicyclo [2.2.2] octane; Or the positively charged ion of the N-substitutive derivative of pyridine, pyrroles, imidazoles, oxazole, pyrimidine, quinoline, isoquinoline 99.9, pyrazine, indoles, benzoglyoxaline, benzoxazole, thiazole, azophenlyene and 2,2 '-bis-pyridine.What other were suitable is cyclic amidines positively charged ion, particularly those are disclosed in as US6, those in 197,849 the 3rd hurdle the 6th row to the 4 hurdles the 67th row.The ammonium compound of ring-type is characterised in that the thermostability of the raising compared with line style ammonium compound.

The layer mineral E1c of preferred cationic exchange is that those skilled in the art are known with term organic clay or nanoclay, and can be purchased, for example, with product group

or

(S ü dchemie AG, Deutschland), (Southern ClayProducts, Inc., USA) or

(Nanocor Inc., USA) obtains.

The layer mineral E1a of anionresin is herein by layer mineral E1 that wherein at least partly negatively charged ion has been exchanged by organic anion " obtain.The example of the layer mineral E1a of this anionoid exchange is that the anion, carbonate in wherein at least a portion middle layer is by the hydrotalcite E1 of organic anion-exchange ".Another example is functionalized aikyiaiurnirsoxan beta (Alumoxane), and it is for example described in US patent 6322890.

Said composition comprises that the layer mineral E1c of cationic exchange and the layer mineral E1a of anionresin are certainly also completely passable simultaneously.

In second embodiment, solid toughness activator is segmented copolymer E2.Negatively charged ion or controlled radical polymerization that segmented copolymer E2 has other monomer of olefinic double bond by methacrylic ester and at least one obtain.Particularly preferred conduct have olefinic double bond monomer be that wherein two keys are directly and heteroatoms or those of other pair of key conjugation with at least one.Specially suitable monomer is selected from vinylbenzene, divinyl, vinyl cyanide and vinyl acetate.Preferred acrylate-Styrene And Chloroalkyl Acrylates (ASA) multipolymer, for example conduct

from GEPlastics Co., USA can obtain.

The segmented copolymer that particularly preferred segmented copolymer E2 is made up of methyl methacrylate, vinylbenzene and divinyl.This based block copolymer for example can triblock copolymer form claim from Arkema with SBM product group name, Inc., and USA obtains.

In the 3rd embodiment, solid toughness activator E is core-shell polymer E3.Core-shell polymer is made up of elastic kernel polymkeric substance (core) and rigid crust polymkeric substance (shell).Specially suitable core-shell polymer is made up of the core of elastic acrylate polymkeric substance or elasticity butadiene polymer, and this core is wrapped up by the rigid crust of the thermoplastic polymer of rigidity.Nucleocapsid structure is by the de-mixed spontaneous formation of segmented copolymer, or the polymerization process of employing emulsion or suspension-polymerization methods is also then carried out grafting and designs.Preferred core-shell polymer is to be called as those of MBS polymkeric substance, and it can be used as trade(brand)name

from Arkema, Inc., USA,

from Rohm and Haas Co., USA or F-351 ^tMfrom Zeon ChemicalsL.P., USA is purchased.

The core shell composite particles particularly preferably existing with dry polymer latex form.These examples are from Wacker Chemie AG, and Deutschland has polysiloxane core and an acrylate shell

by Eliokem, Inc., the radiation crosslinking rubber particles from NEP series that USA produces, or from Lanxess AG, Deutschland's

or from Rohm and Haas Co., USA's

Other of the core-shell polymer providing can comparative example as from Nanoresins AG, Deutschland's

In the 4th specific embodiments, solid toughness activator E is carboxylated solid nitrile rubber and the solid reaction product E4 of excess epoxy resin.

In the 5th embodiment, solid toughness activator E is the soft silica of for example describing in WO 02/083776A1 and WO 2004/081076, and its disclosed content is incorporated herein.This product can be from Nanoresins AG, the trade(brand)name of Deutschland

commercially available.

As the preferably core-shell polymer of solid toughness activator E.

Solid core-shell polymer E3 can be in particular 0.1 to 15% weight in the gross weight based on foam, and the amount that is preferably 1 to 8% weight is present in Thermocurable foam.

In another preferred embodiment, composition additionally also comprises at least one filler F.Described composition epoxy resin, particularly heat-curable epoxy resin composition also advantageously comprise at least one filler F.This is mica, talcum, kaolin, wollastonite, feldspar, syenite, chlorite, wilkinite, polynite, calcium carbonate (precipitation or grind), rhombspar, quartz, silicon-dioxide (pyrolysis method or precipitation), cristobalite, calcium oxide, aluminium hydroxide, magnesium oxide, hollow porcelain bead, Hollow Glass Sphere, organic hollow pearl, granulated glass sphere, colored pigment preferably.Filler F refers to commercially available and well known by persons skilled in the art through organic coat and uncoated form.

The gross weight of the ratio of filler F based on foam is 3 to 50% weight in respect of profit, is preferably 5 to 35% weight, is in particular 5 to 25% weight.

In still another preferred embodiment, composition additionally also comprises that at least one has the reactive diluent G of epoxide group.Particularly preferred reactive diluent G is:

Saturated or unsaturated, the branching of-simple function or the C of non-branching, ring-type or open chain ₄-C ₃₀the glycidyl ether of alcohol, such as butanols glycidyl ether, hexanol glycidyl ether, 2-Ethylhexyl Alcohol glycidyl ether, glycidyl allyl ether, tetrahydrofurfuryl glycidyl ether and furfuryl glycidyl ether, trimethoxysilyl glycidyl ether etc.

Saturated or unsaturated, the branching of-bis-senses or the C of non-branching, ring-type or open chain ₂-C ₃₀the glycidyl ether of alcohol, such as diglycidyl ether of ethylene glycol, butyleneglycol glycidyl ether, hexylene glycol glycidyl ether, ethohexadiol glycidyl ether, cyclohexanedimethanodiglycidyl diglycidyl ether, neopentylglycol diglycidyl ether etc.

-tri-or the glycidyl ether of the alcohol of more polyfunctional, saturated or unsaturated, branching or non-branching, ring-type or open chain, such as epoxidised Viscotrol C, epoxidised TriMethylolPropane(TMP), epoxidised tetramethylolmethane or aliphatic polyol are as many glycidyl ethers of Sorbitol Powder, glycerine, TriMethylolPropane(TMP) etc.

The glycidyl ether of-oxybenzene compound and aniline compound, for example phenyl glycidyl ether, cresyl glycidyl ether, p-tert-butyl-phenyl glycidyl ether, nonyl phenol glycidyl ether, the positive ten pentaene base glycidyl ethers (from cashew nut shell oil) of 3-, N, N-diglycidylaniline etc.

-epoxidised amine is as N, N-diglycidyl hexahydroaniline etc.

-epoxidised list or dicarboxylic acid, the such as 2-glycidyl ester of neodecanoic acid glycidyl ester, glycidyl methacrylate, phenylformic acid glycidyl ester, o-phthalic acid diglycidyl ester, tetrahydrophthalic acid 2-glycidyl ester and hexahydrophthalic acid 2-glycidyl ester, dimer (fatty acid) yl etc.

-epoxidised two or polyether glycol trifunctional, low to high molecular weight, such as polyethyleneglycol diglycidylether, polypropylene glycol diglycidyl ether etc.

Particularly preferably hexanediol diglycidyl ether, cresyl glycidyl ether, p-tert-butyl-phenyl glycidyl ether, polypropylene glycol diglycidyl ether and polyethyleneglycol diglycidylether.

The ratio of reactive diluent G with epoxide group is advantageously gross weight meter 0.5 to 20 % by weight based on foam, preferably 1 to 8 % by weight.

Composition can comprise other composition, is in particular catalyzer, thermo-stabilizer and/or photostabilizer, thixotropic agent, softening agent, solvent, inorganic or organic filler, whipping agent, dyestuff and pigment.

The present invention further comprises the method for the preparation of Thermocurable foam.

The first for the preparation of the method for Thermocurable foam is preferably, 20 to 80 DEG C, particularly under the temperature of 20 to 60 DEG C and barometric point, gas is incorporated into heat-curable composition Z in and sneaked into and be distributed in composition by means of mixing device.In this method, the introducing of gas can be by being for example blown into gas in composition or by the method reducing pressure in mixing equipment and being drawn in composition and carrying out by crossing pressure pipeline.

The preferred method of such one has for example been described in DE 10 2,005 042 380 A1.

Second method for the preparation of Thermocurable foam is, the gas inject with liquid state or supercritical state, in the heat-curable composition Z under pressure, and is sneaked into and is distributed in composition by means of mixing device.Composition is reduced pressure in atmospheric process follow-up, gas expansion and formation foam.

The important point in all two kinds of methods for the preparation of thermoset foam is, composition Z foamed before using, and foaming process substantially finishes in the time of that moment of using.Guarantee only so, composition can accurately apply and in the time that Thermocurable foam is used as tackiness agent, during curing under hot effect, can not occur because the base material to be bonded that foaming process causes moves.

Because composition to be foamed is heat-curable composition Z, so will ensure, the temperature below the solidification value lower than composition foams, no matter and it according to which kind of method carries out.Blowing temperature preferably≤100 DEG C, be in particular 20 to 80 DEG C, more preferably 20 to 60 DEG C.

Preferably heat-curable composition Z and obtainable Thermocurable foam can stably stored at the temperature of≤100 DEG C thus, particularly at room temperature, that is they can be in suitable packaging or configuration, for example, in drum, bag or magazine, store from some months to year and longer for some time, they can the properties at its application feature or after solidifying not change due to chemical reaction in the degree of the use about them simultaneously.

In addition, the present invention includes Thermocurable foam as above as the purposes of tackiness agent, sealing agent or for the preparation of coating and for the purposes with foam-filled hollow structure.Here, Thermocurable foam can be with the single component or the multicomponent system that act on many application schemes.

Especially, Thermocurable foam of the present invention is suitable as for structure bond or connects the hot setting adhesive of (Unterf ü tterung) for vehicle structure median surface.

For bonding be connected heat-stable material with interface for, this tackiness agent is essential.

So-called heat-stable material be interpreted as be those at 100 to 220 DEG C, preferably under the solidification value of 120 to 200 DEG C at least at the stable material of inside dimension set time.These materials refer to that metal and plastics are as ABS (=acrylonitrile-butadiene-styrene (ABS)) especially, polymeric amide, polyphenylene oxide, matrix material is as SMC (=sheet molding mixture), unsaturated polyester GFK (plastics that=glass fibre strengthens), epoxide or acrylate compound material.The application that preferably wherein at least one material is metal.Particularly preferred application is bonding identical or different metal, particularly in the structure of the body shell in automotive industry (Rohbau).The steel of steel, Bonazink-coated steel and the follow-up phosphatization of preferred metal particularly steel, particularly electrogalvanizing, galvanizing (feuerverzinkter), oiling, and aluminium, the various forms particularly generally occurring in automobile construction.

The same preferably sealing agent using Thermocurable foam as thermofixation, is used in particular for sealing flanging and connects and seam.

Adopt Thermocurable foam based on present composition Z, make to provide can for interface connect and the crash-resistant construction adhesive technology of sealing also therefore also obtain there optimum adhesion result becomes possibility.

In addition likely change, the intensity of the foam after the thermofixation of last gained by different foaming degrees.Thus, the Thermocurable foam still with gas with various content of being prepared by identical heat-curable composition Z can be for different objects.Use the direct suitable foaming machine using and mixing equipment before the application equipment of Thermocurable foam time, also can during using, very rapidly change foaming degree.

Adopt tackiness agent, sealing agent or coating based on Thermocurable foam according to the present invention, make to obtain the high strength of expectation and the possibility that is combined into of remarkable lower material cost.

In addition, the present invention includes the method for adhesive substrate S1 and S2, it comprises the following steps:

C1) the Thermocurable foam of as described above is applied on base material S1;

C2) composition that makes to use contacts with the second base material S2;

Or

D1) the Thermocurable foam of as described above is applied on base material S1 and S2;

D2) two kinds of base material S1 and S2 that used foam are engaged.

Wherein, described base material S1 is by forming with the identical or different heat-stable material of base material S2.

The present invention also comprises that it comprises the following steps for the method for sealing substrate S1 and/or S2:

E1) the Thermocurable foam of as described above is applied on base material S1 and/or base material S2;

Or

F1) the Thermocurable foam of as described above is applied between base material S1 and the surface of S2.

Wherein, base material S1 is by forming with the identical or different heat-stable material of base material S2.

The present invention also further comprises the method that adopts foam filling hollow structure, and it comprises the following steps:

G1) the Thermocurable foam of as described above is injected to existing hollow structure.

Here, the foam after thermofixation can be as sealing member and/or for sound insulation and/or for example, for the structural reinforcing of hollow structure, the structural reinforcing of structural element.

The present invention equally also comprises that it comprises the following steps for the preparation of the method for coating or sealing substrate S1:

H1) the Thermocurable foam of as described above is applied to base material S1.

At bonding step c2) and d2) afterwards and the step e1 of sealing) and f1) afterwards, fill the step g 1 of hollow structure with foam) afterwards with the step h1 of coating) carry out afterwards one or several at 100 to 220 DEG C, the particularly curing schedule at 120 to 200 DEG C of temperature.

Another integral part of the present invention is, in preceding method, the gas content of the foaming degree of composition Z and therefore Thermocurable foam of the present invention can change during the using of foam.In order to regulate foaming degree, suitable foaming and application equipment can be controlled by means of suitable software by computer.The advantage that changes foaming degree during using is that having foam of different nature can, by identical application equipment, preferably not use with dismantling.

Fig. 1 illustrate for the preparation of, use and solidify according to the method for Thermocurable foam of the present invention.This method is for two kinds of base materials on bonding production line (Fertigungslinie) for example.In this process, composition Z 1 is transported in mixing equipment M with together with gas from gas container 2, and composition Z 1 and gas mix mutually there.The Thermocurable foam 3 forming thus directly by mixing equipment M by application equipment or be manually coated on base material 4.Then, base material 4 is by Thermocurable foam and the second base material 4 ' engage.Afterwards attachment are heated to the solidification value of Thermocurable foam, wherein Thermocurable foam 3 solidify the foam 3 that obtains through thermofixation '.

The advantage of wherein preparing and use this method that the step of foam directly carries out is continuously, the gas content of Thermocurable foam can change very fast.Therefore, can be prepared into Thermocurable foam by identical composition Z, and this foam is because its different gas content has different character.The using of this Thermocurable foam can entirely and not need by this method to unload application equipment and carry out.

Fig. 2 illustrates the adhesive tape being formed by Thermocurable foams 3 on base material 4, wherein has and shows the part (in circle) of amplifying.Gas is arranged in the chamber or the hole 6 that are evenly dispersed in composition Z.

Fig. 3 has schematically shown the car engine cover before bonding, its by outer metal sheet 5 and be positioned under the former for the rib-like metal sheet 5 that supports '.Thermocurable foam is applied to steelframe 5 ' upper and needn't be unloaded application equipment by application equipment as tackiness agent.According to bonding position, use the foam with gas with various content respectively.Require special high strength and must stand on the position of great machinery load at those, the Thermocurable foam 3a using preferably has low gas content, has the gas content of 10 to 50% volumes.Thermocurable foam only should have on the position of limited textural property therein, for example Thermocurable foam connects as pure interface in the interior region of hood of tackiness agent therein, Thermocurable foam 3b used has high gas content, has the gas content of 30 to 80% volumes.Use the Thermocurable foam 3a with low-gas content and become possibility with those 3b with high gas content by changing the ratio of mixture of composition Z and gas in preparation and application, making to be unloaded equipment by same Whole Equipment.

In addition, the present invention includes as described above the foam through thermofixation obtaining by the step of solidification heat solidified nature foam.

Gas in foam after thermofixation is preferably encapsulated in diameter≤1mm, is in particular≤0.5mm, preferably≤0.1mm and being evenly dispersed in the hole in composition.

In addition, the present invention also comprises the goods that obtained for method bonding, that seal or brush by this.This goods are preferably the appurtenances of vehicle or vehicle, particularly automobile.

In addition, Thermocurable foam of the present invention is not only applicable to automobile construction and is applicable to other purposes field.What mention especially can be the related application in the manufacture of for example steamer, goods stock, motorbus or rail vehicle of the vehicles or in the manufacture of for example washing machine of the consumer's goods.

Embodiment

the preparation of Thermocurable foam

By 300g by Sika Automotive GmbH, the tackiness agent that Deutschland is obtained commercially

be weighed in metal tin, and in the dissolver with 2500 rpms of rotating speeds and 8cm dish diameter, moving up and down under the condition of this tank and stir 7 minutes.Meanwhile, by means of the pressure line under 3bar pressure, pressurized air is blasted in tackiness agent.Keeping under constant mass, density in this process by 1.28kg/m ³be reduced to 1.14kg/m ³, this increases approximately 12% corresponding to volume.Therefore prepared the Thermocurable foam with 12% volumes of air content.

experiment

The Thermocurable foams of preparation are applied on the zinc-plated steel plate being generally used in automobile making by spatula is manual as described above.As reference embodiment, directly will be applied to by it with identical method without the tackiness agent of foaming.Subsequently, test body solidifies 35 minutes in baking oven at 175 DEG C.

Similarly, prepare respectively bonding complex body by two kinds of zinc-plated steel plates and described Thermocurable foam or without the tackiness agent of foaming, after engaging by its in baking oven at 175 DEG C curing 35 minutes.

result

Foam according to the present invention has the extraordinary cementability on base material.In addition, show by the foam cutting after thermofixation, the hole that the air of foam is filled is dispersed in foam very uniformly.

Two kinds of bonding complex bodys of preparation demonstrate very good cementability in wedging test.

Summary of drawings

By means of accompanying drawing, embodiments of the invention are more at large described below.Element identical or that have a same function has identical Reference numeral in different figure.Certainly, the present invention is not limited to the embodiment that says of shown and description.

Accompanying drawing is:

Fig. 1 schematically show for the preparation of, use and solidify according to the method for Thermocurable foam of the present invention;

Fig. 2 schematically shows the cross section through the adhesive tape of Thermocurable foam 3 along the line A-A in Fig. 1;

Fig. 3 schematically show bonding before the hood of automobile, it is by steel plate 5 and be positioned at steelframe 5 under it ' form.

In the drawings, only shown for directly understanding the necessary element of invention.

Reference numerals list

1 composition Z

2 gas containers

3 Thermocurable foaies

3a has the Thermocurable foam of low-gas content

3b has the Thermocurable foam of high gas content

3 ' through the foam of thermofixation

4 attachment/base material S1

4 ' attachment/base material S2

5 hoods/outer metal sheet

5 ' hood/interior metal sheet

6 chambers/aperture

Claims (51)

1. a Thermocurable foam, it consists of the following composition:

A) at least one gas of 10 to 80% volumes; And

B) heat-curable composition Z, it comprises

B1) polyether polyols with reduced unsaturation of at least one formula (I)

Wherein

R ¹by the polyether polyols with reduced unsaturation PU1 of n1+n2+n3 isocyanate groups end-blocking, linear or branching after removing the isocyanate groups of all ends;

R ²be the group of formula (II) independently of each other

R ³be the group of formula (II ') independently of each other;

Wherein R ⁴and R ^{4 '}each is for optionally comprising heteroatomic aliphatics, alicyclic, aromatic series or araliphatic (p+1)-or (f+1)-valency alkyl;

P=1,2 or 3 and f=1,2 or 3;

N1, n2 and n3 are 0 to 7 numerical value, and prerequisite is 2≤(n1+n2+n3)≤8;

B2) at least one is by the solidifying agent B of the temperature-activated of rising;

Described Thermocurable foam can stably stored at the temperature of≤100 DEG C.

2. Thermocurable foam as described in claim 1, is characterized in that described heat-curable composition Z is containing chemical foaming agent.

3. the Thermocurable foam as described in aforementioned claim 1 and 2 any one, is characterized in that heat-curing composition Z additionally also comprises that at least one has the epoxy resin A that per molecule on average exceedes an epoxide group.

4. the Thermocurable foam as described in aforementioned claim 1 and 2 any one, is characterized in that gas is encapsulated in the chamber (6) being evenly distributed in foam.

5. the Thermocurable foam as described in aforementioned claim 1 and 2 any one, is characterized in that polyether polyols with reduced unsaturation PU1 has the polymkeric substance Q of terminal amino group, thiol group or oh group and/or prepared by the phenol optionally replacing by least one polyisocyanates and by least one.

6. as aforementioned Thermocurable foam claimed in claim 3, it is characterized in that the gross weight based on foam, the ratio of epoxy resin A is 2 to 80% weight.

7. as aforementioned Thermocurable foam claimed in claim 6, it is characterized in that the gross weight based on foam, the ratio of epoxy resin A is 5 to 70% weight.

8. as aforementioned Thermocurable foam claimed in claim 6, it is characterized in that the gross weight based on foam, the ratio of epoxy resin A is 7 to 60% weight.

9. the Thermocurable foam as described in aforementioned claim 1 and 2 any one, is characterized in that the gross weight based on foam, and the ratio of the polyether polyols with reduced unsaturation of formula (I) is 5 to 50% weight.

10. the Thermocurable foam as described in aforementioned claim 1 and 2 any one, is characterized in that the gross weight based on foam, and the ratio of the polyether polyols with reduced unsaturation of formula (I) is 10 to 40% weight.

11. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that the gross weight based on foam, and the ratio of the polyether polyols with reduced unsaturation of formula (I) is 15 to 35% weight.

12. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that the gross weight based on foam, and the ratio of solidifying agent B is 0.5 to 8% weight.

13. Thermocurable foaies as described in aforementioned claim 12, is characterized in that the gross weight based on foam, and the ratio of solidifying agent B is 1 to 6% weight.

14. Thermocurable foaies as described in aforementioned claim 12, is characterized in that the gross weight based on foam, and the ratio of solidifying agent B is 2.5 to 5% weight.

15. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that the gross weight based on foam, and solidifying agent B is that catalyzer and its ratio are 0.05 to 2% weight.

16. Thermocurable foaies as described in aforementioned claim 15, is characterized in that the gross weight based on foam, and solidifying agent B is that catalyzer and its ratio are 0.1 to 1% weight.

17. Thermocurable foaies as described in aforementioned claim 15, is characterized in that the gross weight based on foam, and solidifying agent B is that catalyzer and its ratio are 0.2 to 0.75% weight.

18. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that described gas is selected from nitrogen (N ₂), carbonic acid gas (CO ₂), hydrogen (H ₂), carbon monoxide (CO), laughing gas (N ₂o), any mixture of rare gas and these gases.

19. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that described gas is selected from gaseous mixture.

20. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that described gas is selected from air.

21. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that described gas is selected from nitrogen or air.

22. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that foam additionally also contains at least one filler, and based on the gross weight of foam, its amount is 1 to 50% weight.

23. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that foam additionally also contains at least one filler, and based on the gross weight of foam, its amount is 5 to 40% weight.

24. Thermocurable foaies as described in aforementioned claim 1 and 2 any one, is characterized in that foam additionally also contains at least one filler, and based on the gross weight of foam, its amount is 10 to 35% weight.

The method of the Thermocurable foam of 25. preparations as described in claim 1 to 24 any one, is characterized in that

-under the temperature of 20 to 80 DEG C and barometric point, gas is introduced in heat-curable composition Z, and sneaked into and be distributed in described composition by means of mixing equipment;

Or

-by the gas inject existing with liquid or supercritical state in the heat-curable composition Z under pressure, sneaked into and be distributed in composition Z by means of mixing equipment, and in the time subsequently composition being reduced pressure expand to such an extent as to form foam.

26. methods as claimed in claim 25, is characterized in that under the temperature of 20 to 60 DEG C and barometric point, gas being introduced in heat-curable composition Z, and are sneaked into and be distributed in described composition by means of mixing equipment.

27. Thermocurable foaies as described in claim 1 to 24 any one are as tackiness agent, sealing agent, for the preparation of coating or for fill the purposes of hollow structure with foam.

28. purposes as claimed in claim 27, are used as Thermocurable tackiness agent.

29. purposes as claimed in claim 28, connect for structure bond or for the interface of vehicle structure.

30. purposes as claimed in claim 27, are used as Thermocurable sealing agent.

31. purposes as claimed in claim 30, for sealed folded connection and seam.

32. 1 kinds of methods for adhesive substrate S1 and S2, it comprises the following steps:

C1) the Thermocurable foam as described in claim 1 to 24 any one is applied on base material S1;

C2) used Thermocurable foam is contacted with the second base material S2;

Or

D1) the Thermocurable foam as described in claim 1 to 24 any one is applied on base material S1 and S2;

D2) two kinds of base material S1 and S2 that applied foam are engaged;

Wherein, described base material S1 is by forming with the identical or different heat-stable material of base material S2; With

Wherein at step c2) or steps d 2) carry out afterwards one or more at the temperature of 100 to 220 DEG C curing step.

33. methods as claimed in claim 32, wherein at step c2) or steps d 2) carry out afterwards one or more at the temperature of 120 to 200 DEG C curing step.

34. 1 kinds of methods for sealing substrate S1 and/or S2, it comprises the following steps:

E1) the Thermocurable foam as described in claim 1 to 24 any one is applied on base material S1 and/or base material S2;

Or

F1) the Thermocurable foam as described in claim 1 to 24 any one is applied between base material S1 and the surface of S2;

Wherein, base material S1 is by forming with the identical or different heat-stable material of base material S2; And

Wherein at step e1) or step f1) carry out afterwards one or more at the temperature of 100 to 220 DEG C curing step.

35. methods as claimed in claim 34, wherein at step e1) or step f1) carry out afterwards one or more at the temperature of 120 to 200 DEG C curing step.

36. 1 kinds of methods that use foam to fill hollow structure, it comprises the following steps:

G1) the Thermocurable foam as described in claim 1 to 24 any one is injected to the hollow structure existing;

Wherein in step g 1) carry out afterwards one or more at the temperature of 100 to 220 DEG C curing step.

37. methods as claimed in claim 36, wherein in step g 1) carry out afterwards one or more at the temperature of 120 to 200 DEG C curing step.

38. 1 kinds for the preparation of coating or for the method for sealing substrate S1, it comprises the following steps:

H1) the Thermocurable foam as described in claim 1 to 24 any one is applied on base material S1;

Wherein at step h1) carry out afterwards one or more at the temperature of 100 to 220 DEG C curing step.

39. methods as claimed in claim 38, wherein at step h1) carry out afterwards one or more at the temperature of 120 to 200 DEG C curing step.

Method described in 40. claim 32 to 39 any one, it is characterized in that the foaming degree of composition Z and therefore the gas content of the Thermocurable foam as described in claim 1 to 24 any one can during using foam, change.

The foam of 41. 1 kinds of thermofixations, is characterized in that it is obtained by the Thermocurable foam as described in claim 1 to 24 any one.

42. Thermocurable foaies as claimed in claim 41, is characterized in that gas is encapsulated in have≤1mm diameter and is evenly distributed in the hole in composition.

43. Thermocurable foaies as claimed in claim 41, is characterized in that gas is encapsulated in have≤0.5mm diameter and is evenly distributed in the hole in composition.

44. Thermocurable foaies as claimed in claim 41, is characterized in that gas is encapsulated in have≤0.1mm diameter and is evenly distributed in the hole in composition.

45. 1 kinds of bonding by the method as described in claim 32 to 39 any one, to seal, obtain with foam filling or coating goods.

46. goods as claimed in claim 45, is characterized in that these goods are the vehicles or the consumer's goods.

47. goods as claimed in claim 45, is characterized in that these goods are vehicles.

48. goods as claimed in claim 45, is characterized in that these goods are automobiles.

49. goods as claimed in claim 45, is characterized in that these goods are steamer, goods stock, motorbus, rail vehicle.

50. Thermocurable foaies as claimed in claim 1, is characterized in that, gas content is 10 to 50% volumes.

51. Thermocurable foaies as claimed in claim 1, is characterized in that, gas content is 30 to 80% volumes.

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